Novel bleaching compounds

ABSTRACT

WHEREIN R IS AN ALKYL, ARYL OR SUBSTITUTED ARYL GROUP, X IS BROMINE OR CHLORINE, AND M IS AN ALKALI METAL, ARE USEFUL AS BLEACHING AGENTS AND AS DISINFECTANTS.   R-SO2-N(-X)-(CH2)2-SO3-M   N-HALOGENATED COMPOUNDS HAVING THE GENERAL FORMULA

United States Patent O 3,711,413 NOVEL BLEACHING COMPOUNDS Peter Robson,Nortliumherland, and Frederick Edward Hardy, Newcastle-upon-Tyne,England, assignors to The Procter & Gamble Company, Cincinnati, Ohio NoDrawing. Original application Oct. 9, 1968, Ser. No. 766,326. Dividedand this application Mar. 10, 1972, Ser. No. 233,791

Int. Cl. Clld 7/56 US. Cl. 252-99 9 Claims ABSTRACT OF THE DISCLOSUREN-halogenated compounds having the general formula R-S O 2l |T( C H2)s-S03M wherein R is an alkyl, aryl or substituted aryl group, X is bromineor chlorine, and M is an alkali metal, are useful as bleaching agentsand as disinfectants.

BACKGROUND OF THE INVENTION This is a division of application Ser. No.766,326, filed Oct. 9, 1968, now US. Pat. No. 3,654,348.

The use of various N-halo organic compounds as bleaching agents and asdisinfectants is known. Compounds which have been suggested for thesepurposes are, for example, dichloroand dibromo-cyanuric acid and theirsalts, trichlorocyanuric acid, and 1,3-dichloroand 1,3-dibromo-5,S-dimethylhydantoin. The preferred halo compounds are usually chosen forstability and for usefulness solely on the basis of halogen release insolution. These compounds hydrolyze readily in aqueous solution toproduce hypochlorite or hypobromite ions which are well known asbleaching agents, and they have advantages over well-known peroxybleaching agents in that they bleach effectively at low temperatures(below 80 C.).

SUMMARY OF THE. INVENTION Applicants have now discovered a novel classof compounds, namely N-chloro and N-bromo compounds of the generalformula which are good bleaching agents, and further, are capable ofetfectively removing stains from fabrics at temperatures under 80 C.Additionally, these compounds exhibit the property of beinganti-bacterial agents, thereby making them suitable disinfectants aswell.

The novel compounds can be prepared, without difiiculty, by one ofseveral reactions dependent on the type or nature of the startingmaterial used. For example, use of an alkali metal derivative of asulfonamide as a starting material yields the corresponding novelcompound in a simple two-step reaction procedure; on the other hand, useof a N-halo aryl sulfonamide as a starting material yields thecorresponding novel compound in a one-step reaction procedure.

The nature of R in the general formula can be widely varied to include,as specific examples, alkyl radicals, aryl radicals, and aryl radicalssubstituted with alkyl groups or halides. Further, the aryl radical canbe mono-nuclear or di-nuclear.

Applicants have also found that these novel bleaching compounds canreadily and effectively be used in granular bleaching compositions and,also, in granular detergent compositions, the other constituents of suchcompositions being known in the art to great detail.

3,711,413 Patented Jan. 16, 1973 DESCRIPTION OF THE INVENTIONAccordingly, the invention provides N-bromo and N- chloro compounds ofthe general formula:

wherein R is an alkyl, aryl or substituted aryl radical, X is chlorineor bromine, and M is an alkali metal such as Na, K or Li. Preferably Ris an alkyl radical with 1 to 18 carbon atoms, or an unsubstitutedmonoor di-nuclear aryl radical, or a monoor di-nuclear aryl radicalsubstituted by one or more electron-donating or electronwithdrawinggroups which groups, if alkyl, contain 1 to 14 carbon atoms. Examples ofsuitable electron-donating groups include, but are not limited to, thefollowing: nalkyl, sec-alkyl, iso-alkyl, and tert-alkyl groups of from 1to 14 carbon atoms; C H and substituted derivatives (e.g., OCHg).Examples of suitable electron-withdrawing groups include, but are notlimited to, the following: NO -X (where X=bromine and chlorine);--'COOI-I; COR; -SO I-I; CN; and, -NQCH The new compounds can beprepared by (1) reacting the alkali metal derivative of a sulfonamidewith 1,3- propane-sultone and then (2) reacting the intermediatecompound so formed with a solution of hypochlorous or hyprobromous acidaccording to the following equations:

R-SOz-NH-Na OH1CH2CHZ SE0.

R-SOz-NHUJHDQSO NQ RSOzNH(OHz);SO Na x R-SOzIf-(CHzJg-SOz-Na H10 whereinR and X have the meanings given above.

An alternative method of preparation of the compounds in which R is anaryl or substituted aryl radical, which avoids use of organic solvents,is to react the sodiurn salt of an N-chloroor N-bromoaryl, orsubstituted-aryl, sulfonamide having the general formula R-S Oz-IIIN8[X= chlorine or bromine] with propane sultone in aqueous solution; R canbe the simple benzene radical or a benzene radical substituted, forexample, with a chloride ion or a methyl group.

The N-bromo-compounds may also be made by reacting the appropriate novelN-chloro'compound with bromide 1011.

The following examples serve to illustrate the invention herein and donot limit it. Additional examples, within the scope of this invention,will be apparent to those skilled in the art. In all examples, anypercentages given therein are by weight, unless otherwise stated.

EXAMPLE I Preparation of sodium N-chloro-N-(benzenesulfonyl)-3-aminopropan-l-sulfonate 71 g. of benzenesulfonamide were dissolved inmethanol, and a solution of sodium methoxide (from 3.63 g.

of sodium) in methanol was added, giving a molar ratio of sulfonamide tosodium methoxide of substantially 3:1. The mixture was evaporated todryness, and the solid residue was suspended in 600 ml. of toluene. Thesuspension was dried by distilling off 50 ml. of toluene; 21.1 g. of1,3-propanesultone was added, giving a molar ratio of sodiumbenzenesulfonamide to 1,3-propanesultone of substantially 1:1. Themixture was boiled under reflux for four hours and was then allowed tostand overnight. The solid product was filtered off and dissolved inwater. The aqueous solution was neutralized with sulfuric acid andevaporated to dryness. The residue was washed with acetone and thendissolved in a boiling ethanol/water (95/5 v./v.) mixture. On coolingand filtering, 23 g. of sodiumN-(benzenesulfonyl)-3-aminopropan-1-sulfonate were recovered.

This compound was dissolved in 500 ml. of 0.22 M hypochlorous acidsolution and allowed to stand for 30 minutes. The solution wasevaporated to 50 ml. and cooled. The crystalline precipitate wasfiltered off and dried to yield 22.5 g. of sodiumN-chloro-N-(benzenesulfonyl)-3aminopropanl-sulfonate monohydrate.

EXAMPLE II Preparation of sodium N-chloro-N-(dodecanesulfonyl)-3-aminopropan-l-sulfonate Dodecanesulfonamide (14.8 g.) was treated withsodium methoxide (from 0.46 gm. sodium, giving a ratio of sulphonamideto sodium methoxide of substantially 3:1) and then with1,3-propanesultone (2.6 g.) as described in Example 1. On cooling, thegelatinous mass was stirred with acetone (200 ml.), and the product wasfiltered.

Recrystallization from 95%? ethanol gave 6 g. of sodiumN-(dodecanesulfonyl)-3-aminopropan-l-sulfonate.

1.6 g. of this intermediate compound--i.e., sodiumN-(dhdecanesulfonyD-F;-aminopropan-l-sulfonate, having the generalformula of RAO NH(CH SO M wherein R is the dodecyl radicalwere dissolvedin hot water (25 ml.), and the solution was added dropwise into 20.5 ml.of 0.32 M hypochlorous acid. The mixture was stirred at room temperaturefor 10 minutes and cooled. Filtration and drying gave 1.5 g. of sodiumN-chloro N (dodecanesulfonyl) 3 aminopropan-lsulfonate.

When R is aryl or substituted aryl, the said intermediate compound (forreaction with hypochlorous or hypobromous acid) can also be made byreacting alkali metal 3- aminopropan-1-sulfonate with an aromaticsulfonyl chloride of the general formula RS O C1, wherein R is anaromatic or substituted aromatic radical as described above.

EXAMPLE HI Preparation of sodium N-ehloro-N- (p-toluenesulfonyl)-3-aminopropan-l-sulfonate 1,3-propanesultone (10 g.) was added dropwiseto aqueous ammonium hydroxide (200 ml. d., 0.88). The solution wasstirred at room temperature for 30 minutes, heated on a steam bath for 1hour, and evaporated to dryness.

The crystalline residue (11.1 g.) was dissolved in aqueous sodiumhydroxide (6.25 g. in 1001111. and the solution was concentrated invacuo to evaporate liberated ammonia. p-Toluenesulfonyl chloride (12.6g.) was added, and the mixture was stirred at 65-75 C. for 2 hours untilit had become homogeneous. This solution was neutralized and evaporatedto dryness; the residue was extracted with boiling ethanol-water (9:1v./v.). Evaporation of the extract gave sodium N-(p-toluenesulfonyD-3-aminopropan-l-sulfonate (20.5 g.).

This material was dissolved in aqueous hypochlorous acid (380 ml.; 0.21M). After 30 minutes the solution was concentrated in vacuo and cooled.The crystalline mass (17 g.) was filtered, dried and found to consist ofsodium N-ichloro N (p-toluene'sulfonyl) 3 aminopropan-lsulfonate.

EXAMPLE IV Preparation of sodium N-bromo-N-(p-toluenesulfonyl)-3-aminopropan-l-sulfonate Propanesultone (10 g.) was added dropwise toaqueous ammonium hydroxide (200 ml., d., 0.88). The solution was stirredat room temperature for 3 0 minutes, heated on a steam bath for 1 hourand evaporated to dryness.

The crystalline residue (11 g.) was dissolved in aqueous sodiumhydroxide (6.25 g. in 100 ml.), and the solution was concentrated invacuo to evaporate liberated ammonia. p-Toluenesulfonyl chloride (12.6g.) was added and the mixture stirred at 65-75 C. for 2 hours, until itbecame homogeneous. This solution was neutralized and evaporated todryness, and the residue was extracted with boiling acetone-water (95:5;100 1111.). Cooling of the extract, followed by the addition of ethanolcaused precipitation of sodiumN-(p-toluenesulfonyl)-3-aminopropan-l-sulfonate (15 g.) which wasfiltered and dried.

This material was dissolved in hypobromous acid (166 ml., 0.29 M), andafter 15 minutes the solution was conoentrated and cooled. The highlycrystalline N-bromo-N- (p-toluensulfonyl) 3-aminopropan-l-sulfonate(10.2 g.) was filtered and dried.

EXAMPLE V 10 g. of chloramine T (sodium N-chloro-p-toluenesu'lfonamidetrihydrate) was dissolved in the minimum necessary quantity of water at60 C.; 4.78 g. of 1,3- propanesultone were added, and the mixture wasstirred for 30 minutes. On cooling to room temperature, a crystallineprecipitate was formed which was filtered oil and dried, providing 9 g.of sodium N-chloro-N-(p-toluenesulfonyl)-3-arninopropan-1-sulfonatemonohydrate.

EXAMPLE VI When molecular equivalent amounts of the sodium derivativesof N-chlorobenzene sulfonamide, or N-chlorop-chlorobenzenesulifonamide,are substituted for the sodium N-chlorotoluenesulfonamide of Example V,the corresponding compounds in which R is C H and ClC H are obtained.

Bleach tests were carried out on test pieces of tea-stained cotton clothin 18 hard water at 50 C., the water containing 0.2% sodiumtripolyphosphate and an amount of bleaching agent sufiicient to supply35 parts per million available chlorine in the bleach liquor; thesetests showed that the new N-chloro compounds bleach as efiectively assodium hypochlorite.

The term available chlorine, as used herein, refers to the amount ofmolecular chlorine (C1 having equal bleaching power. Since one atom ofactive chlorine in these N-chloro compounds, and in hypochlorites, hasthe same activity as one molecule of molecular chlorine (i.e. twoatoms), the percentage available chlorine stated, by weight, is doublethe weight percentage of reactive chlorine in the molecule. Thus, sodiumN-chloro-N-(benzene sulfonyl)-3-aminopropan-l-sulfonate monohydrate,having the formula C H SO N(Cl) (CH- SO Na'H O, contains 10% actualchlorine by weight, expressed as 20% available chlorine.

The new N-chloro and N-bromo compounds oi this invention are suitablefor use in the formulation of granular bleaching and detergentcompositions and can be conveniently mixed with water-soluble inorganicand organic alkaline salts or with water-soluble organic detergentcompounds, or with both.

Water-soluble alkaline inorganic salts which are suitable for use inconjunction with these new compounds are alkali metal carbonates,borates, phosphates, polyphosphates, bicarbonates, silicates, andsulfates. Specific examples include sodium and potassium pyrophosphateand tn'polyphosphate, disodium orthoplrosphate. sodium and potassiumhexametaphosphates, trisodium orthophosphate, sodium and potassiumcarbonate and bicarbonates, sodium sesquicarbonate, sodium and potassiumperborates and tetraborates, and various sodium silicates. Otherinorganic alkaline, neutral or acidic salts may be included as fillersor for processing reasons. The corresponding salts of other alkalimetals may be substituted for part or all of the sodium salts.Particularly suitable salts are sodium pyrophophate and sodiumtripolyphosphate, sodium bicarbonate, and disodium orthophosp-hate.

Examples of suitable organic alkaline builder salts are: (1)water-soluble aminopolyacetates, e.g., sodium and potassiumethylenediaminetetraacetates, nitrilotriacetates, andN-(2-hydroxyethyl)-nitrilo diacetates; (2) Watersoluble salts of phyticacid, e.g., sodium and potassium phytates (see US. Pat. 2,739,942); (3)Water-soluble polyphosphonates, including specifically, sodium,potassium and lithium salts of (a) ethane-l-hydroxy-l,l-diphosphonicacid, (b) methylene disphosphonic acid, and (c) ethane-1,1,2-triphosphonic acid; other examples include alkali metal salts ofethane-2-carboxy-1,l-diphosphonic acid, hydroxymethanediphosphonic acid,carbonyl diphosphonic acid, ethane-l-hydroxy-l,1,2-triphosphonic acid,ethane2- hydroxy-1,1,2-triphosphonic acid,propane-1,1,3,3-tetraphosphonic acid, propane-1,1,2,3-tetraphosphonicacid, and propane-1,2,2,3-tetraphosphonic acid; (4) Water-soluble saltsof polycarboxylate polymers and copolymers as described in the patent ofFrancis L. Diehl, U.S. 3,308,067 issued Mar. 7, 1967, e.g., itaconicacid, aconitic acid, maleic acid, citraconic acid, mesaconic acid,sumaric acid, methylene malonic acid, and copolymers with themselves andother compatible monomers such as ethylene.

Examples of water-soluble detergent compounds which can be used in thebleaching compositions of this invention includes, but are not limitedto, the following:

(a) anionic synthetic detergents, as represented by sodium alkylsulfates, sodium or potassium alkylbenzenesulfonates, sodiumalkylglycerylethersulfonates, and others;

(b) nonionic synthetic detergents, as represented by polyethylene oxidecondensates of alkylphenols; condensation products of aliphatic alcoholsof 8 to 18 carbon atoms with ethylene oxide; long chain tertiary amineoxides corresponding to the general formula wherein R is an alkylradical of about 8 to 18 carbon atoms with R and R being methyl or ethylradicals; long chain tertiary phosphine oxides corresponding to thegeneral formula R R R P 0, wherein R is an alkyl, alkenyl ormonohydroxyalkyl radical of about to 18 carbon atoms with R and R beingalkyl or monohydroxyalkyl groups of 1 to 3 carbon atoms;

(0) ampholytic synthetic detergents, as represented by the derivativesof aliphatic amines which contain about 8 to 18 carbon atoms and ananionic water solubilizing group (e.g., carboxy, sulfo, sulfato); and,

(d) Zwitterionic synthetic detergents, represented by derivatives ofaliphatic quaternary ammonium compounds, wherein one of the aliphaticgroups has about 8 to 18 carbon atoms, another contains awater-solubilizing group, and any of which are straight or branched.

The anionic, nonionic, ampholytic, and Zwitterionic detergents may beused singly or in combination together with the present invention. Withregard to these detergents, a more complete disclosure may be found inFrancis Diehl, US. Pat. 3,213,030, issued Oct. 19, 1965, lines 53 to 75of column 3, lines 1 to 75 of column 4, and lines 1 to 30 of column 5,and said disclosure is hereby incorporated by reference hereinto.

In granular bleaching compositions, the N-chloro or N-bromo compound mayconstitute up to 90% or more by weight of the total composition, or itmay constitute less than 1% of the total composition; the balancecomprises a Water-soluble alkaline salt. Generally, a N-chloro orN-bromo compound is included in an amount which provides from 0.5 to 8%,preferably about 4%, by Weight of available chlorine in the composition,or, on a corresponding molar basis, from about 1 to 18%, preferablyabout 9%, of active bromine. A detergent compound, if employed, usuallyconstitutes up to 25% by weight of the composition, preferably 1% to10%. The pH of such bleaching compositions (as measured in a 1% solutionof the composition) is generally in the range 7 to 11, preferably 8.5 to10.5.

EXAMPLE VII Salt NaHCOa NaaPzOm Na|P 01 NaZCOB Approximate pH 8. 6 9. 39. 7 10. 7 Percent stain removal. 45. 5 60 69 70 Detergent compositions,in which a novel compound of the invention herein is a component, alsocomprise both a Water-soluble organic detergent and a water-solubleinorganic or organic alkaline builder salt. In such compositions, thenovel compounds herein can be present in an amount ranging from 0.5% to25%. The amount of detergent can range, from about 1% to about 50%,preferably from about 5% to about 25%, and the ratio of detergent tobuilder salt is, preferably, in the range of 4:1 to 1:20; and, thecomposition, preferably, has a pH range of 8 to 11.

EXAMPLE VIII A suitable heavy duty detergent composition, providing a pHof 9.5, has the formulation:

This product is particularly suitable for washing soiled white goods(e.g. table linen and bed linen) at normal Washing machine temperatures(-175 F., especially about F.), and it is not necessary to use the hightemperatures (200 F. to boiling) which are required for effectivebleaching with sodium perborate as the bleaching agent. Substantiallyequivalent results are obtained if the sodium N-chloro-N-(benzenesulfonyl)-3-aminopropan-1- sulfonate in the above formula is replaced byan equal Weight of the corresponding N-chloro-N-(p-toluenesulfonyl)-,N-chloro-N-(p-chlorobenzenesulfonyl-, N-chloro-N- (methanesulfonyl) orN-bromo-N-(p-toluenesulfonyl)-3- aminopropan-l-sulfonates.

The new N-halo compounds of the invention are, also, valuable as stainremoving agents in abrasive hard surface cleanser compositions. Theyhave very good bactericidal properties and can be used in theformulation of disinfectant and sanitizing compositions. For example,they can be included in dishwashing compositions for use in automaticdishwashing machines, in which they serve both to prevent proteinspotting and as sanitizing agents.

Detergent, bleaching, and sanitizing compositions containing the newcompounds of the invention can, additionally, contain the normal minoringredients often added to such compositions, such as suds boosters,soil suspending agents, corrosion inhibitors, halogen-stable opticalbrighteners, colors, and perfumes. Among the suitable perfume 7materials are terpenic and non-terpenic compounds which contain in themolecule a double bond between two carbon atoms, one of which is atertiary carbon atom.

Additional examples, further illustrating the utility of the inventionherein, are as follows:

EXAMPLE IX Four dry granular bleaching compositions were made, using thefollowing components:

Percent by weight Sodium N-chloro-N-(benzenesulfonyl) 3aminopropan-l-sulfonate Water-soluble, inorganic alkaline salt 80 Thesalts used in each composition were the same as those given in ExampleVII. The compositions were then placed into water to give solutions thesame in concentrations as in Example VII. The same tea stain removaltests, under the same conditions, as given in Example VII, were run, andthe results were the same as given therein.

This example further illustrates the ease with which the novel N-chloroand N-bromo compounds can readily be used in granular bleachingformulations, and it demonstrates the stain removing ability of thenovel compounds contained in such compositions.

EXAMPLE X It is known in the art that detergent compositions whichcontain a combination of sodium tripolyphosphate (STP) and sodium saltsof nitrilotriacetic acid (NTA) greatly enhance cleansing ability andmaintenance of whiteness. (See Burton H. Gedge, US. Pat. 3,356,613issued Dec. 5, 1967.) The novel N-halo compounds are suitable for use insuch granular built detergents and serve to more efiectively providecleaning and whitening ability. Formulations of such granulardetergents, containing the novel N-bromo and N-chloro compounds, have apH range of 8 to 11 and are:

Formulation 1 A B C D um near dodec l benzene sulfuiiiitef 13. 3 10Reaction product of S03 and a a-olefins neutralized with NaOH 20Condensation reaction product of 1 mole of tallov algglllol and 10 molesof 10 x1 N' l fi i iinish i 9. 9 14. 3 24. 1 STP 41. 2 40 30. 7 22. 9Sodium carboxymethyl cellulose- 0. 33 1. 6 Sodium random octadccylphosphonate- 0. 1 0. 1 Sodium sulfate 11 14 20 11 Sodium silicate (SiOz:NazO =1 .6: 1) 6 10 10 Sodium salt of marine fatty acid g Sodium saltof tallow fatty acids. Benzotriazole Optical brightener (optional)Coloring (optional) 3 Perfume (optional) 4N-chloro-N-(benzenesulionyl)-3- 7 7 aminopropan-l-sulionate 7 7 Water 1Fi ures in the columns are percentages by weight. 2 Tlie range isvariable and generally runs from 0.1% to 1% by weight. 8 The range isvariable and only traces are used, usually amounting to less than 0.5 byWeight.

4 The rangz is variable and generally runs from 0.1% to 1% by weight.

5 Balance.

Sodium linear dodecylbenzene-sulfonate 7 NTA 50 Sodium carbonate 10Sodium silicate 10 Water Balance 8 EXAMPLE XII An effective dry,granular, scouring cleanser composition, having bleaching anddisinfecting characteristics and conveniently containing a novel N-bromoor N-chloro compound, is as follows:

(1) from about 0.1% to about 4%, by weight, of a novel N-chloro compoundor from about 0.5% to about 9% of a novel N-bromo compound;

(2) from about 0.1% to about 10%, by weight, of a compatiblewater-soluble organic detergent;

(3) from about 2.5% to about 30%, by weight, of a water-soluble alkalinedetergency builder (organic or inorganic); and,

(4) from about 60% to by weight, of water-insoluble abrasive material.

The scouring cleanser formulations are most effective when used at a pHlevel of from 9 to 12. Examples of suitable detergents for use in thesescouring cleanser compositions include those described on pages 10, l1and 12 of the specification herein; suitable water-soluble alkalinebuilder salts include those disclosed herein'on pages 9 and 10. Examplesof water-insoluble abrasives, suitable for use in the scouring cleansercompositions of the invention herein, include finely divided particulatesiliceous abrasives such as silica, feldspar, pumice, volcanic ash,diatomaceous earth, bentonite, talc, and the like. A suitable particlesize for the abrasive material ranges from about 0.03 mm. diameter toabout 0.001 mm. diameter and finer.

An optional component of such scouring cleanser compositions is perfume,which if added, generally ranges from about 0.1 to about 1% by weight.

Suitable specific scouring cleanser compositions, containing novelN-chloro or N-bromo compounds, are as follows:

Composition 1 1 All figures are expressed in percentages by weight.

The specifications herein have disclosed that the novel N-bromo andN-chloro compounds can readily and conveniently be used in granulardetergent, bleaching and scouring cleanser compositions. Suchcompositions are substantially dry, i.e., solid compositions which aredry to the touch and substantially devoid of uncombined moisture.Accordingly, the composition can contain components in a hydratable form(anhydrous or partially hydrated). Thus, the water-soluble inorganicalkaline salt used can be in the hydratable form, as Well as the novelN-chloro and N-bromo compounds themselves, and no change in theeffectiveness or utility of the novel compounds occurs.

Therefore, what is claimed is:

1. A granular detergent composition consisting essentially of from 0.5%to 25% of a novel bleaching compound having the formula wherein M is analkali metal selected from the group consisting of sodium, potassium,and lithium, X is chlorine or bromine, and R is selected from the groupconsisting of alkyl of from 1 to 18 carbon atoms; phenyl; andsubstituted-phenyl; the substituent of said substitutedphenyl beingselected from the group consisting of alkyl of from 1 to 14 carbonatoms; C H --0CH -N0 chloro; bromo; -COOH; SO H; -CN; and

3)a a Water-soluble inorganic or organic alkaline builder salt; and awater-soluble organic detergent; the ratio of detergent to builder saltbeing in the range of 4:1 to 1:20. 2. The granular detergent compositionof claim 1 wherein the novel bleaching compound is selected from sodiumN-chloro-N- (benzenesulfonyl) -3-aminopropanel-sulfonate, sodiumN-chloro-N-(dodecanesulfonyl)-3-aminopropanel-sulfonate,

sodium N-chloro-N- (p-toluenesulfonyl) -3-arninopropanel-sulfonate,

sodium N-bromo-N- (p-toluenesulfonyl)-3-arninopropane-l-sulfonate, or

sodium N-chloro-N-(p-toluenesulfonyl)-3-aminopropanel-sulfonatemonohydrate.

3. The granular detergent composition of claim 1 wherein thewater-soluble inorganic salt is selected from the group consisting ofalkali metal carbonates, borates, phosphates, polyphosphates,bicarbonates, silicates or sulfates.

4. The granular detergent composition of claim 1 wherein the buildersalt is a water-soluble organic salt selected from the group consistingof aminopolyacetates, sodium and potassium phytates, polyphosphonates,or the water-soluble polycarboxylate salts.

5. The granular detergent composition of claim 1 wherein thewater-soluble detergent is selected from the group consisting of thesodium alkyl sulfates, sodium or potassium alkylbenzenesu'lfonates andsodium alkylglycerylethersulfonates, wherein the alkyl group containsfrom 8 to 18 carbon atoms.

6. Granular detergent compositions of claim 1 in which the water-solublesynthetic detergent is a nonionic detergent selected from the groupconsisting of (1) polyethylene oxide condensates of alkyl phenols,condensation products of alcohols of 8 to 18 carbon atoms with ethyleneoxide, (2) long chain tertiary amines of the formula wherein R is analkyl radical of about 8 to 18 carbon atoms with R and R being methyl orethyl radicals, or long chain tertiary phosphine oxides of the formulawherein R is an alkyl, alkenyl or monohydroxy-alkyl radical of from 10to 18 carbon atoms with R and R being alkyl or monohydroxy-alkylcontaining from 1 to 3 carbon atoms.

7. The granular detergent composition of claim 1 wherein thewater-soluble synthetic detergent is an ampholytic detergent selectedfrom derivatives of amines having from 8 to 18 carbon atoms and ananionic watersolubilizing group such as the carboxy, sulfo, and sulfatoradicals.

8. The granular detergent composition of claim 1 wherein thewater-soluble synthetic detergent is a Zwitterionic detergent selectedfrom the aliphatic quaternary ammonium compounds where the aliphaticgroups have from 8 to 18 carbon atoms.

9. A granular bleaching composition consisting essentially of from 0.5%to preferably about 4% of a compound in accordance with the formula ofclaim 1; and a water-soluble inorganic or organic alkaline salt of from0.5% to 25% preferably 1% to 10% by weight of the composition.

References Cited UNITED STATES PATENTS 2,694,727 11/1954 Cross et al.260-508 2,394,902 2/ 1946 Engelmann 260-556 2,809,937 10/ 1957 Gray252-422 OTHER REFERENCES Fischer, Propane-Sultone, Industrial andEngineering Chemistry, vol. 56, No. 3, pp. 41-45 (March 1964).

Suter, The Organic Chemistry of Sulfur, John Wiley and Sons, New York,N.Y. (1964), p. 603.

MAYER WEINBLATI, Primary Examiner US. Cl. X.R. 52-94, 102, 106, 187;260-508 R; 424-149

